Maintenance Guide

Sensor Performance
Titrant Performance &
Standardization

Day-to-Day Routine Maintenance

of Automatic Titrators

Content

Content
1

Introduction

Instrument Installation

The Effects of Temperature on the Results

Sensor Performance

Titrants Performance

Sample Size

Titrant Standarization

More Information

11

12

15

Disclaimer
The information contained in this guide is based on the current knowledge and experience of the authors. The
guide represents selected, possible application examples. The experiments were conducted and the resulting
data evaluated in our lab with the utmost care using the instruments specified in the description of each
application. The experiments were conducted and the resulting data evaluated based on our current state of
knowledge.However, this guide does not absolve you from personally testing its suitability for your intended
methods, instruments and purposes. As the use and transfer of an application example are beyond our control,
we cannot accept responsibility therefore.
When chemicals, solvents and gases are used, the general safety rules and the instructions given by the
manufacturer or supplier must be observed.

METTLERTOLEDO

Titration Routine Maintenance

Introduction

1. Introduction
Analytical instruments need regular maintenance to ensure proper working conditions and finally correct results.
One part of maintenance is concerned with instrument adjustment, certification and the like. Here manufacturer's
service engineers are due to take actions.
Another part are checks which are carried out by the users or an instrument responsible person. They are
performed frequently, on a daily or weekly base. The purpose of these checks is mainly to show whether the
instrument still performs according to expectation. If deviations occur, the check outcomes indicate correction
measures to the users.
For titrators, such maintenance tasks include its installation arrangement, the influence of temperature, the
sensor functionality, the titrant status and considerations regarding the sample size.

METTLERTOLEDO

Titration Routine Maintenance

Instrument Installation

2. Instrument Installation
Professional installation is fundamental to every analytical system. Depending on the requirements, the right
level of measures needs to be applied. The measures encompass the following 4 topics.
GLP
International bodies have elaborated a set of rules concerning the analytical work in labs in order to achieve
a standard regulation recognized and accepted in all countries of the world. These rules are commonly known
as GLP rules (Good Laboratory Practice). GLP is a formal framework for testing chemicals and consists of
10 specific rules.
Certification of an automatic titrator
The certification is a check of the instrument in order to verify that the technical specifications are fulfilled,
or to verify if the actual specifications meet the required level.
Certification is only part of a list of measures to guarantee correct results.
Validation of Titration Methods
While the goal of the analysis is to get correct results, very often the correct result is not necessarily the true
result. As a result, our goal is in fact to get the best possible result. This means a result as accurate, precise and
true as possible. To do this its important to critically investigate the factors affecting each of these things and
minimize the negative influences.
Qualification
Quality management requires the documentation of the performance over the lifetime of the instrument, i.e., from
the project phase through manufacturing, installation and operation through disposal of the instrument. All these
steps are resumed in the comprehensive concept of qualification:
Specification Qualification (SQ): Requirements, Functions, Design, HW/SW
Construction Qualification (CQ): Production control for each product
Design Qualification (DQ): Selection of correct instrument for intended use
Installation Qualification (IQ): Evidence of correct installation at customers facility
Operational Qualification (OQ): Evidence and compliance to specifications, SOPs, initial calibration,
user training
Performance Qualification (PQ): Periodic performance tests
Maintenance Qualification (MQ): Definition of preventive maintenance and calibration/certification intervals
Specially trained METTLER TOLEDO service engineers are able to perform the calibration and certification of the
titrator hardware with specific calibrated and certified tools (CertiCase, Excellence Test Unit).
Recommendations
Have the titration system installed by the instrument manufacturers specialist.
Perform a General System Suitability Test, proving that the titrator is performing according to the specifications.
Apply the concept of qualifications.

METTLERTOLEDO

Titration Routine Maintenance

Instrument Installation
Figure 1: Lab titrator family

METTLERTOLEDO

Titration Routine Maintenance

The Effects of Temperature on the Results

3. The Effects of Temperature on the Results

Temperature can have three different effects on a titration.
The first effect is related to the density, and therefore the concentration of the titrant. The effect is due to the
coefficient of thermal expansion. This is of particular significance with non-aqueous titrants where the coefficient
of thermal expansion is much higher than with deionized water. Below is a table showing typical errors.
The second becomes apparent when performing an endpoint titration to a predefined pH value. The pH of the
sample depends on the degree of dissociation of the acids and bases present. The dissociation is temperature
dependent. Thus, a temperature change gives rise to a real change in the pH value. This change cannot be
accounted for without knowing the samples exact composition.
A further effect concerns the actual measurement process and the slope of the electrode calibration curve.
The slope of the calibration curve is temperature dependent so it is important to either perform the analysis at the
same temperature at which the electrode was adjusted, or to measure both temperatures and compensate for
the change in slope of the calibration curve. Fortunately, most modern instruments are able to simultaneously
measure the sample temperature and automatically compensate for this error.
Titrant

% Error per C change

0.1 M NaOH

0.027

1 M NaOH

0.036

0.1 M HCl

0.026

1 M HCl

0.029

1 component 5 mg/mL Karl Fischer Reagent

0.092

Table 1: Error in concentration due to temperature change.

Recommendations
The best solution is to maintain constant temperature in the laboratory e.g. by air condition. Air condition
prevents temperature shifts.
Keep samples in the same place as titrants to ensure the same termperature. If the titrant concentration
(i.e. titer determination) and samples are measured at the same temperature then there is no error.
Do not expose the instrument to direct sunlight. Place it in a protected area.
Measure the temperature when performing pH measurements or end point titrations.
- METTLER TOLEDO offers pH sensors with integrated temperature probes for this purpose.
Use certified pH buffers for sensor calibration and apply their temperature table.
- METTLER TOLEDO titrators and pH meters automatically offer this possibility.
Perform titrant standardization when the temperature changes significantly. Re-standardizing reduces errors
due to temperature changes considerably.
Apply a temperature correction factor: Measure the temperature of the titrant and correct for the temperataure
change.
Example: Karl Fischer reagent, 10C temperature difference in the lab

f = 1 + (Ttiter Tsample) x CONC-ERR

CON C-ERR = 0.092 / 100 = 0.00092
TT TS = -10

f = 1 10 x 0.00092 = 0.9908
Multiplying raw results by this factor will account for the error.

METTLERTOLEDO

Titration Routine Maintenance

Sensor Performance

4. Sensor Performance
In pH endpoint titrations, critical factors affecting result accuracy are the slope and zero point of the sensor.
Both of these parameters are used to convert the raw mV signal from the sensor into the pH of the sample
solution using the Nernst equation:

pH = pHo E
S
E
S
pH0

, where

= measured signal (in mV)

= sensor slope
= 2.3 RT / nF
= sensor zero point
= E0/S

Since sensors are the actual measurement devices, they have a very large influence on the result of any
titration. Several factors contribute to their behaviour:
Response: If a sensor is sluggish because of old age or bad maintenance, the mV reading detected by the
sensor will lag behind the true value.
Calibration: Sensor calibration is particularly important for endpoint titrations (mainly pH endpoints). The
accuracy of the measured value is directly related to the determined amount of the analyte content in the sample.
Every maintenance procedure performed on a sensor (cleaning, regeneration, etc.), requires that the sensor
be calibrated again.
For pH, we recommend to apply a two or three point calibration. If samples are usually around 7, three
calibration points at pH 4, 7 and 9 (or 10) are good practice. This ensures that pH values below and above
7 are measured correctly. If the samples are acidic, a two point calibration between 4 and 7 is usually
acceptable and yields reliable results.

mV

real

pH

ideal

Figure 2: Schematic of a three-point pH calibration.

Reference electrode: A reference electrode has to provide a stable reference signal against which the
measurement signal is determined.
Conditioning: The measuring membrane of any pH or ion selective electrode needs to be conditioned before
the sensor can be used.

METTLERTOLEDO

Titration Routine Maintenance

Sensor Performance

When a pH sensor is used in non-aqueous media, the sensor needs to be conditioned before its next use to
restore the hydration layer.
Recommendations
Define a sensor calibration frequency to make sure that the sensor is measuring correctly, e.g. at least once
per day.
Instead of frequent calibrations, a sensor check can be performed. Such a check shows that the sensor is
still functioning correctly but it does not change calibration data. The sensor check should include the signal
drift over one minute, which is an important indication of the response time and signal stability. Use pH buffer
4 or 9 as a sample for this check.
Take the appropriate measures to automatically remind users to calibrate.
- METTLER TOLEDO Excellence titrators offer the functionality of monitoring sensors life span as well as usable
life. When a calibration needs to be performed or the sensor needs replacing, the user is automatically
reminded. A sensor can even be blocked from use if the setting is chosen accordingly.
Define acceptance limits for the calibration results.
- All METTLER TOLEDO titrators allow these limits to be set in the method. If the limit is exceeded, the user is
prompted and the calibration data is not saved.
When not in use, sensors should be stored in electrolyte.

Figure 3: Details of the measuring membrane of pH electrodes.

METTLERTOLEDO

Titration Routine Maintenance

Titrants Performance

5. Titrants Performance
The concentration of a titrant needs to be known accurately to be able to determine the content of analyte in the
sample solution. If the titrant concentration is unknown or inaccurate, there will inevitably be a degree of error.
Titer
From the determined titrant concentration and the nominal titrant concentration, a titer value t is calculated. The
titer is the ratio of determined concentration / nominal concentration and is generally close to 1.

t = current titrant concentration / nominal titrant concentration
Example:
Current titrant concentration, by determination: 0.1036 mol/L

Nominal titrant concentration, by declaration: 0.1 mol/L
Titer t = 0.1036 / 0.1 = 1.036
For titer determinations, a primary standard is preferable. A primary standard is a substance that reacts with the
titrant in a known ratio ("stoichimetrically"). Its purity is high and well defined. It is very stable and has a high
molecular weight.
Examples of primary standards:

Tris-hydroxy amino methane (THAM) for acids,

Potassium hydrogen phthalate (KHP) for bases,
NaCl or KCl for argentometry

Titrant life time

Titrants can deteriorate over time through various external influences like oxidation, precipitation, carbon dioxide
absorption or UV degradation. We can account for some of these by using drying tubes filled with NaOH on
carrier material (CO2 absorption in alkaline titrants) or with brown bottles (light protection).
The rate of deterioration determines how long the titrant can be used before re-standardizing. This is called
the usable life of the titrant. After the usable life has expired, a new titer determination should be performed
before running subsequent analyses. In most titrators, the usable life of a specific titrant can be defined and
standardization intervals can be enforced before being allowed to continue.
The lifespan of a titrant is the time after which a titrant should be replaced. The lifespan is different for every
type of titrant. For example, acids are more stable than alkaline titrants and can have a life span of up to a year,
compared to 6 months for a base. During the lifespan, regular standardization should be performed to guarantee
reliable results.
Recommendations
Define a standardization frequency ensuring titrant concentration (titer t) is correct.
Define a titrant life span.
Take the appropriate measures to automatically remind users to perform a standardization, preventing usage
of a titrant with an exceeded usable life.
- METTLER TOLEDO Excellence titrators offer the functionality of monitoring titrants, automatically warn and
remind users and block unfit titrants from use.
Define acceptance limits for the titer determination, e.g. 0.96 t 1.05
- All METTLER TOLEDO titrators allow these limits to be set in the standardization method. If the limit is
exceeded, the user is prompted and the new titer value will not be saved.
Prepare and store titrants with care.

METTLERTOLEDO

Titration Routine Maintenance

Titrants Performance

In the case of alkaline titrants such as sodium and potassium hydroxide, its important that they are prepared
with water or solvent free of carbon dioxide, and that they are protected from atmospheric exposure to carbon
dioxide. Attach a drying tube containing an absorbent (e.g. NaOH on a granular carrier) to the titrant bottle.
Titrants such as iodine, permanganate and dichromate are light sensitive and need to be protected by storing
them in brown glass bottles. Karl Fischer reagents need to be protected from light as well as from the ingress
of atmospheric humidity. This is done by attaching a drying tube containing silica gel or molecular sieve to
the titrant bottle.

Figure 4: Automatic titrator with 5 titrants (burettes)

METTLERTOLEDO

Titration Routine Maintenance

10

Sample Size

6. Sample Size
By far, the biggest source of random errors resulting in precision problems is sample handling. These errors
include inhomogeneity of the sample, sample storage problems, incorrect sample size, weighing errors, and
careless handling. Critical in most cases is the sample size.
The sample should be large enough to ensure that it is representative, but it shouldnt be so large that repeated
burette fillings are necessary during the titration. The ideal sample size should give a titrant consumption of 30
to 80% of a single burette volume.
On the other extreme, the sample should be large enough so that weighing or sample measuring errors are kept
to a minimum. Here, a suitable balance must be used to ensure that the sample size exceeds the minimum
weight of the balance. This minimum weight is defined as the weight which when measured tenfold, results in a
repeatability of less than a certain pre-defined value; for example, United States Pharmacopoeia (USP) states
a value of less than 0.1%.
The sample volume including deionized water and/or other solvents that is used for any titration should be
sufficient to cover the sensors active parts (junction and sensing membrane or metal ring). Normally, this
volume should be around 50 mL to be able to fit the stirrer, titration tubes and dosing tubes in with the probe.
For smaller sample sizes, special micro-titration beakers can be used.
Recommendations
Make sure that you're using the needed balance resolution for your sample size. The accuracy and precision
of the sample size must be smaller than the expected accuracy and precision of the titration result.
For solid samples, use a calibrated analytical balance with 0.1 mg or 0.01 mg readability.
For liquid samples use a calibrated high quality Rainin pipette.
Choose a sample size that consumes 30 to 80% of the burettes volume. The sample size, titrant concentration
or burette size can be changed to reach this goal
Dilute the sample with an appropriate solvent volume to make sure the active parts of the equipment are
covered (approximately 50 mL). If necessary, use micro-titration equipment.

METTLERTOLEDO

Titration Routine Maintenance

11

Titrant Standardization Overview

7. Titrant Standardization Overview

Solvent and
Auxiliary reagents

Frequence of
Standarization

Protection of Titrant /
General Remarks

DG111SC

Deion. H2O

weekly

Protect from CO2

(absorption
tube filled with
NaOH on carrier
granulate)

M002

DG111SC

Deion. H2O

weekly

Protect from CO2

(absorption
tube filled with
NaOH on carrier
granulate)

Benzoic acid
C7H6O2; M =
122.12

M010

DG115SC
LiCl 1M
in EtOH

Isopropanol

weekly

Protect from CO2

(absorption
tube filled with
NaOH on carrier
granulate)

Sodium methylate Benzoic acid

c(NaOCH3) =
C7H6O2; M =
0.1 mol/L
122.12

M026

DG115SC
LiCl 1M
in EtOH

Methanol

daily

Protect from CO2

(absorption
tube filled with
NaOH on carrier
granulate)

Potassium
hydroxide
c(KOH) = 0.1
mol/L

Benzoic acid
C7H6O2; M =
122.12

M027

DG115SC
LiCl 1M
in EtOH

Ethanol

weekly

Protect from CO2

(absorption
tube filled with
NaOH on carrier
granulate)

Sulfuric acid
c(1/2 H2SO4) =
0.1 mol/L

Tris(hydroxymethyl)aminomethane [THAM]
C4H11NO3; M = 121.14
g/mol

M011

DG111SC

Deion. H2O

every 2
weeks

Hydrochloric
acid
c(HCl) = 0.1
mol/L

Tris(hydroxymethyl)aminomethane
[THAM] C4H11NO3; M
= 121.14 g/mol

M003

DG111SC

Deion. H2O

every 2
weeks

Perchloric acid
c(HClO4) = 0.1
mol/L

Tris(hydroxymethyl)aminomethane [THAM]
C4H11NO3; M = 121.14
g/mol

M005

DG115SC
LiCl 1M
in EtOH

Acetic acid

weekly

Titrant

Standard Substance

Method

Indication

Sodium hydroxide Potassium

c(NaOH) = 1.0
hydrogen
mol/L
phthalate
C8H5KO4;
M = 204.23

M025

Sodium hydroxide Potassium

c(NaOH) = 0.1
hydrogen
mol/L
phthalate
C8H5KO4;
M = 204.23
Tetrabutyl
ammonium
hydroxide
c(TBAH) = 0.1
mol/L

Alkalimetry

Acidimetry

Table 2: Alkalimetric and acidimetric titrants.

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Titration Routine Maintenance

12

Titrant Standardization Overview

Titrant

Frequence of
Standarization

Protection of Titrant /
General Remarks

DM141- Deion. H2O

SC
acidify to pH
3.5

every 2
weeks

Keep bottle in
dark

M028

DM141- Deion. H2O

SC
acidify to pH
3.5

every 2
weeks

M024

DP550

Deion. H2O
Buffer pH 4
Thorin

weekly

Standard Substance

Method

Indication

Silver nitrate
c(AgNO3) = 0.1
mol/L

Sodium chloride
NaCl; M =
58.44

M006

Sodium chloride
c(NaCl) = 0.1
mol/L

Silver nitrate
AgNO3;
M=169.89

Barium chloride
c(BaCl2) = 0.1
mol/L

Sodium sulfate
Na2SO4; M =
142.05

Solvent and
Auxiliary reagents

Precipitation

Complexometry
Complexone III
c(EDTA) = 0.1
mol/L

Zink sulfate
ZnSO4; M =
161.44

M007

DP660

Deion. H2O
Buffer pH 10,5
Indicator Erio T

every 2
weeks

Use PE bottles

Complexone III
c(EDTA) = 0.1
mol/L

Calcium
carbonate
CaCO3; M =
100.09

M022

DP660

Deion. H2O
Indicator buffer
tablet MERCK

every 2
weeks

Use PE bottles

Complexone VI
c(EGTA) = 0.1
mol/L

Calcium
carbonate
CaCO3; M =
100.09

M014

DP660

Deion. H2O
Indicator buffer
tablet MERCK

every 2
weeks

Use PE bottles

Zink sulfate
c(ZnSO4) = 0.1
mol/L

EDTA . 2H2O
EDTA ;
M=372.24

M029

DP660

Deion. H2O
Buffer pH 10,5
Indicator Erio T

every 2
weeks

Use PE bottles

Barium perchlorate
c(Ba(ClO4)2) = 0.005
mol/L

EDTA . 2H2O
EDTA ; M=372.24

M023

DP550

Deion. H2O /
methanol NH3
solution 5%
Indicator
Phthaleinpurpur

weekly

Use PE bottles

Table 3: Precipitation and complexometric titrants.

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Titration Routine Maintenance

13

Titrant Standardization Overview

Titrant

Standard Substance

Method

Indication

Solvent and
Auxiliary reagents

Frequence of
Standarization

Protection of Titrant /
General Remarks

Redox Titration (Reducing titrants)

Sodium thiosulfate
c(Na2S2O3) =
0.1 mol/L

Potassium iodate
KIO3;
M = 214.00 g/mol

M009

DM140-SC

Hydrochloric
acid 0.1 M

every 2 weeks

Hydroquinone
c(C6H6O2)= 0.1 mol/L

Potassium
dichromate
K2Cr2O7;
M = 294.19 g/mol

M017

DM140-SC

Sulfuric acid 5%

weekly

Keep bottle in dark

Ammonium ferrous (II)

sulfate
c(FAS) = 0.1 mol/L

Potassium
dichromate
K2Cr2O7;
M = 294.19 g/mol

M008

DM140-SC

Sulfuric acid 5%

daily

Protect from Oxygen

Redox Titration (Oxidizing titrants)

Iron(III) chloride
c(FeCl3) = 0.1 mol/L

Ascorbic acid
C6H8O6;
M = 176.13 g/mol

M030

DM140-SC

Deion. H2O

every 2 weeks

Potassium dichromate
c(1/6 K2Cr2O7) =
0.1 mol/L

(CH2NH3)2SO4
FeSO4 4H2O
M = 382.15

M031

DM140-SC

Sulfuric acid 5%

every 2 weeks

Iodine
c(1/2 I2) = 0.1 mol/L

di-Arsenic trioxide
As2O3;
M = 197.84 g/mol

M016

DM140-SC
DG111-SC

Deion. H2O
NaHCO3

daily

Cerium sulfate
c(Ce(SO4)2) =
0.1 mol/L

di-Sodium oxalate
C2Na2O4;
M=134.00 g/mol

M015

DG140-SC

Deion. H2O
Sulfuric acid 5%

every 2 weeks

Potassium
permanganate
c(1/5 KMnO4) =
0.1 mol/L

di-Sodium oxalate
C2Na2O4;
M=134.00 g/mol

M013

DG140-SC

Sulfuric acid 5%
70 C

every 2 weeks

Sodium nitrite
c(NaNO2) =
0.1 mol/L

Sulfanilic acid
C6H7NO3S;
M = 173.19 g/mol

M032

DM140-SC

HBr 0,5 mol/L

weekly

Fehling solution

Glucose 1% in
water C6H12O6;
M = 180.16 g/mol

M033

Combi
Pt-ring
(Ingold)

Deion. H2O

weekly

Prepare Glucose
solution daily.

2,6-Dichlorophenolindophenol Na- salt

c(DPI) = 0.01 mol/L

Ascorbic acid
C6H8O6;
M = 176.13 g/mol

M021

DM142 mit
DK102

Deion. H2O

daily

Keep bottle in dark.

Keep in PE bottles.
Keep cool.

Keep bottle in dark.

Keep cool.

Keep bottle in dark

Table 4: Redox titrants.

Titrant

Standard Substance

Method

Indication

Solvent and
Auxiliary reagents

Frequence of
Standarization

Protection of Titrant /
General Remarks

Turbidimetric Titrations
Sodium dodecylsulfate
c(SDS) = 0.01 mol/L

N-Cetylpyridinium
chloride [CPC]
M = 358.01 g/mol

M035

DP550

Deion. H2O

every 2 weeks

Rinse bottle and

beakers with deion.
water before use

Hyamine c(Hyamine)
= 0.01 mol/L

Sodium
dodecylsulfate
[SDS];
M = 288.4 g/mol

M036

DP550

Deion. H2O

every 2 weeks

Rinse bottle and

beakers with deion.
water before use

N-Cetylpyridinium
chloride c(CPC) =
0.01 mol/L

Sodium
dodecylsulfate
[SDS];
M = 288.4 g/mol

M012

DP660

Deion. H2O

every 2 weeks

Rinse bottle and

beakers with deion.
water before use

Table 5: Turbidimetric Titrations

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Titration Routine Maintenance

14

More Information

8. More Information
7.1 Brochures
GTP Risk Checker, Mettler-Toledo Analytical, 10/2010
Validation of Titration Methods, Application Brochure 16, Mettler-Toledo Analytical, 03/2015, 51724912A
7.2 Webinars
We provide web-based seminars (webinars) on different topics. You can participate in on-demand webinars
at any convenient time and place.
Live webinars offer the added benefit of allowing you to ask questions and discuss points of interest with
METTLER TOLEDO specialists and other participants.
www.mt.com/webinars
7.3 Applications and UserComs
We offer comprehensive titration application support
Titration applications

www.mt.com/titration_applications

Titration UserCom

www.mt.com/anachem-usercom

7.4 Product News

Visit our titration landing page to get informed about the latest product news.
www.mt.com/Titration
7.5 Lab Library
The Lab Library is a one-stop portal to access knowledge resources such as webinars, literature, product info
and much more.
www.mt.com/Lab-Library

METTLERTOLEDO

Titration Routine Maintenance

15

Good Titration Practice

Five Steps to Improved Results
GTP Good Titration Practice
Dependable Titration in Practice Reliable Results with GTP. A requirementsbased selection of the titration system, as well as professional installation and
training form the basis for dependable and risk-free titration.
GTP reduces the risks associated with titration and facilitates
compliance with regulations
preservation of the accuracy and precision of results
increased productivity and reduced costs
professional qualification and training
www.mt.com/gtp

5
Routine
Operation

Calibration /
Qualication

1
Evaluation

Good
Measuring
Practices

2
Selection

3
Installation /
Training

More Good Measuring Practices

Other Good Measuring Practices are available
for weighing, pipetting, density and refractive
index determination, thermal analysis, melting
and dropping point determination as well as
pH, conductivity, dissolved oxygen and redox
measurements.
www.mt.com/gp

www.mt.com
For more information

Mettler-Toledo Intenational Inc.

Laboratory Division
CH-8606 Greifensee, Switzerland

Subject to technical changes

06/2015 Mettler-Toledo AG
Global MarCom Switzerland / MC